JP2005320490A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition having good curability, storability and fluidity, and a semiconductor device excellent in soldering crack resistance and reliability of moisture resistance. <P>SOLUTION: The epoxy resin composition comprises (A) a compound having two or more epoxy groups in one molecule, (B) a compound having two or more phenolic hydroxy groups in one molecule, and (C) an organosilane compound represented by general formula (1). In formula (1), R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>, which may be the same or different, indicate each any one of a 1-4C alkyl group, a 1-4C alkoxy group or a 6-12C aryl group; R<SP>4</SP>indicates a 1-6C hydrocarbon group; R<SP>5</SP>indicates an n-valent organic group; and n is an integer of 1-3. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an epoxy resin composition and a semiconductor device.

  As a method of manufacturing a semiconductor device by sealing semiconductor elements such as IC and LSI, a method of sealing by transfer molding using an epoxy resin composition is low in cost and suitable for mass production. Widely used. In addition, when improving the characteristics and reliability of these semiconductor devices, in the epoxy resin composition, study the types of epoxy resins and phenol resins that are curing agents, and add various organosilane coupling agents. Things have been done.

  However, in recent electronic equipment market trends, as devices become smaller, lighter, and have higher performance, higher integration of semiconductors has been progressing year by year, and in the manufacturing process, surface mounting of semiconductor devices has also been promoted. Accordingly, demands for epoxy resin compositions used for sealing semiconductor elements have become increasingly severe. For this reason, the conventional epoxy resin composition also has a problem that cannot be solved (cannot be handled).

  In recent years, with the shift to the surface mounting method using lead-free solder, the miniaturization / thinning of the semiconductor package, and the diversification of the package shape, further improvement in the solder resistance of the semiconductor sealing material is required.

  In particular, peeling of the chip interface has become a problem along with internal cracks that occur during moisture absorption reflow accompanying the rise in mounting temperature, and improvement in the adhesion between the sealing material and the substrate interface has been required. Yes.

  A method of adding a mercapto-based or amine-based silane coupling agent is used for the purpose of improving the adhesion and improving the solder resistance (see, for example, Patent Documents 1 and 2).

  However, these mercapto-based and amine-based coupling agents have a substituent having high reactivity with an epoxy group, so that in the presence of a curing accelerator generally blended in a resin composition, it can be stored at low temperatures. There is a problem that the curing reaction of the epoxy resin is accelerated and the storage stability of the sealing material is lowered. Because of this, strict quality control when mixing various components, storage and transportation at low temperatures, and strict control of molding conditions are essential, and handling becomes very complicated, improving solder resistance. In addition to this, improvement in preservability has been demanded for the purpose of improving handling during distribution and storage.

Japanese Patent No. 2803057 (No. 2 to 3) Japanese Patent Laid-Open No. 11-60905 (pages 2 to 4)

  An object of the present invention is to provide an epoxy resin composition excellent in storage stability and adhesion, and a semiconductor device excellent in solder crack resistance and moisture resistance reliability.

  As a result of intensive studies to solve the above-described problems, the present inventors have found the following matters and have completed the present invention.

  That is, by adding a specific organic silane compound as an adhesion-imparting component to the epoxy resin composition, the resin composition has excellent storage stability, and electronic parts such as semiconductor elements are sealed with a cured product of the above epoxy resin composition. It has been found that even when the semiconductor device that is stopped is exposed to high temperatures, defects such as cracks and peeling are unlikely to occur.

  That is, the present invention is achieved by the following (1) to (6).

［式中、Ｒ¹、Ｒ²およびＲ³は、炭素数が１〜４のアルキル基、炭素数が１〜４のアルコキシ基、または炭素数が６〜１２のアリール基のいずれかを表し、互いに同一であっても異なっていてもよい。Ｒ⁴は、炭素数が１〜６の炭化水素基を表し、Ｒ⁵はｎ価の有機基を表す。ｎは１〜３の整数を表す。］ (1) Compound (A) having two or more epoxy groups in one molecule, compound (B) having two or more phenolic hydroxyl groups in one molecule, and organic silane compound (C) represented by the general formula (1) ) As an essential component.

[Wherein R ¹ , R ² and R ³ represent any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, They may be the same or different. R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms, and R ⁵ represents an n-valent organic group. n represents an integer of 1 to 3. ]

［式中、Ｒ⁶、Ｒ⁷、Ｒ⁸およびＲ⁹は、それぞれ、水素原子、炭素数１〜６の鎖状もしくは環状アルキル基、フェニル基およびハロゲン原子から選択される１種を表し、互いに同一であっても異なっていてもよい。］

［式中、Ｒ¹⁰〜Ｒ¹⁷は、それぞれ、水素原子、炭素数１〜４のアルキル基およびハロゲン原子から選択される１種を表し、互いに同一であっても異なっていてもよい。ただし、ａは、１〜１０の整数である。］ (2) The compound (A) having two or more epoxy groups in one molecule includes at least one of an epoxy resin represented by the following general formula (2) and an epoxy resin represented by the following general formula (3). The epoxy resin composition according to (1), which is a main component.

[Wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ each represent one selected from a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, They may be the same or different. ]

[Wherein, R ^{10 to} R ¹⁷ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, a is an integer of 1-10. ]

［式中、Ｒ¹⁸〜Ｒ²¹は、それぞれ、水素原子、炭素数１〜４のアルキル基およびハロゲン原子から選択される１種を表し、互いに同一であっても異なっていてもよい。ただし、ｂは、１〜１０の整数である。］

［式中、Ｒ²²〜Ｒ²⁹は、それぞれ、水素原子、炭素数１〜４のアルキル基およびハロゲン原子から選択される１種を表し、互いに同一であっても異なっていてもよい。ただし、ｃは、１〜１０の整数である。］ (3) The compound (B) having two or more phenolic hydroxyl groups in one molecule is at least one of a phenol resin represented by the following general formula (4) and a phenol resin represented by the following general formula (5). The epoxy resin composition according to the above (1) or (2), comprising as a main component.

[Wherein, R ^{18 to} R ²¹ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, b is an integer of 1-10. ]

[Wherein, R ^{22 to} R ²⁹ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same as or different from each other. However, c is an integer of 1-10. ]

(4) The epoxy resin composition according to any one of (1) to (3), which includes an inorganic filler (D).

(5) The content of the inorganic filler is the sum of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule. The epoxy resin composition according to the above (4), which is 200 to 2400 parts by weight per 100 parts by weight.

(6) A semiconductor device comprising an electronic component sealed with a cured product of the epoxy resin composition according to (5).

  The epoxy resin composition of the present invention is excellent in storage stability and adhesion, and the semiconductor device sealed using the epoxy resin composition of the present invention is cracked, peeled off, etc. even when exposed to high temperatures. It is difficult to cause defects.

  Hereinafter, preferred embodiments of the epoxy resin composition and the semiconductor device of the present invention will be described.

  The epoxy resin composition of the present embodiment includes a compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, and a silane compound having a specific structure. (C). Such an epoxy resin composition is excellent in storage stability. In addition, a semiconductor device encapsulated with the epoxy resin composition is less prone to defects such as cracks and peeling even when exposed to high temperatures.

Hereinafter, each component will be sequentially described.
[Compound (A)]
The compound (A) having two or more epoxy groups in one molecule used in the present invention is not limited as long as it has two or more epoxy groups in one molecule.

  Examples of the compound (A) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol type epoxy resins and the like, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, and stilbene type epoxy resins. Such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin and dihydroxybenzene type epoxy resin. Epoxy compounds produced by reacting phosphorus, epoxy resins obtained by oxidizing olefins with peracids, glycidyl ester type epoxy resins and glycidyl amine type resins Carboxymethyl resins and the like, and these can be used singly or in combination of two or more of them.

  Among these, the compound (A) particularly includes one or both of the biphenyl type epoxy resin represented by the general formula (2) and the biphenyl aralkyl type epoxy resin represented by the general formula (3). It is preferable to use the main component. Thereby, the fluidity at the time of molding of the epoxy resin composition (for example, at the time of manufacturing a semiconductor device) is improved, and the solder crack resistance of the obtained semiconductor device is further improved.

  Here, “improvement of solder crack resistance” means that the obtained semiconductor device is exposed to high temperatures in, for example, a solder dipping or solder reflow process, even if the cured product is cracked or peeled off. This means that the occurrence of defects is less likely to occur.

Here, the substituents R ^{6 to} R ⁹ in the biphenyl type epoxy resin represented by the general formula (2) are each a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom. Represents one selected from the above, and these may be the same or different.

As these substituents R ^{6 to} R ⁹ , in addition to a hydrogen atom and a phenyl group, for example, as a chain or cyclic alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, and Examples of the halogen atom include a chlorine atom and a bromine atom. Among these, a methyl group is particularly preferable. Thereby, the melt viscosity of the epoxy resin composition is lowered, and the handling becomes easy, for example, at the time of manufacturing a semiconductor device. In addition, since the water absorption of the cured product is reduced, the obtained semiconductor device is preferably prevented from deterioration over time (for example, occurrence of disconnection) of the internal members, and the moisture resistance reliability is further improved. .

Moreover, the substituents R ^{10 to} R ¹⁷ in the biphenyl aralkyl type epoxy resin represented by the general formula (3) represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, These may be the same as or different from each other.

Examples of these substituents R ^{10 to} R ¹⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a chlorine atom, and a bromine atom. Among these, a hydrogen atom or a methyl group is particularly preferable. Is preferred. As a result, the melt viscosity of the epoxy resin composition is lowered, and for example, when the semiconductor device is manufactured, the handling becomes easy, and the moisture resistance reliability of the semiconductor device is further improved.

  Moreover, a in the said General formula (3) represents the average repeating number of an epoxy resin unit. That is, a is preferably in the range of 1 to 10, more preferably about 1 to 5. By setting a in the above range, the fluidity of the epoxy resin composition is further improved.

[Compound (B)]
The compound (B) having two or more phenolic hydroxyl groups in one molecule used in the present invention has two or more phenolic hydroxyl groups in one molecule and acts as a curing agent for the compound (A) (function). )

  Examples of the compound (B) include phenol novolak resin, cresol novolak resin, bisphenol resin, phenol aralkyl resin, biphenyl aralkyl resin, trisphenol resin, xylylene modified novolak resin, terpene modified novolak resin and dicyclopentadiene modified phenol resin. 1 type or 2 types or more of these can be used in combination.

  Among these, the compound (B) is mainly composed of one or both of the phenol aralkyl resin represented by the general formula (4) and the biphenyl aralkyl resin represented by the general formula (5). It is preferable to use those that do. Thereby, the fluidity at the time of molding of the epoxy resin composition (for example, during the production of a semiconductor device) is improved, and the solder crack resistance and moisture resistance reliability of the obtained semiconductor device are further improved.

Here, the substituents R ^{18 to} R ²¹ in the phenol aralkyl resin represented by the general formula (4) and the substituents R ^{22 to} R ²⁹ in the biphenyl aralkyl resin represented by the general formula (5) are: Each represents one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a halogen atom, and these may be the same or different from each other.

Examples of these substituents R ^{18 to} R ²¹ and R ^{22 to} R ²⁹ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a chlorine atom, and a bromine atom. Among these, a hydrogen atom or a methyl group is particularly preferable. Since such a phenol resin has a low melt viscosity per se, even when contained in the epoxy resin composition, the melt viscosity of the epoxy resin composition can be kept low. Moreover, the handling becomes easy. Moreover, the water absorption (hygroscopicity) of the cured product of the epoxy resin composition (obtained semiconductor device) is reduced, and the moisture resistance reliability is further improved, and the solder crack resistance is also improved.

  Moreover, b in the said General formula (4) and c in the said General formula (5) represent the average repeating number of a phenol resin unit, respectively. That is, b and c each preferably have a range of 1 to 10, more preferably about 1 to 5. By setting each of b and c within the above ranges, a decrease in fluidity of the epoxy resin composition is preferably prevented or suppressed.

[Compound (C)]
The organosilane compound (C) used in the present invention is a compound having 1 to 3 vinylene sulfide structures and is represented by the general formula (1). These function as an adhesion imparting component between the resin composition and the metal substrate by interacting with the metal substrate, including chemical bonds, without impairing the storage stability.

Here, in the general formula (1), the substituents R ¹ , R ^2, and R ³ bonded to the silicon atom are an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or carbon It represents any of 6 to 12 aryl groups, which may be the same or different.

Examples of these substituents R ^{1 to} R ³ include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. C6-C12 aryl groups, such as a C1-C4 alkoxy group, a phenyl group, a naphthyl group, and a biphenyl group, are mentioned, Among these, a methoxy group is more preferable.

In the general formula (1), the substituent R ⁴ bonded to the silicon atom and the aromatic group R ⁵ represents a hydrocarbon group having 1 to 6 carbon atoms.

Examples of these substituents R ⁴ include alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. Among these, a trimethylene group is more preferable.

In the general formula (1), R ⁵ represents a substituted or unsubstituted n-valent organic group, and n represents an integer of 1 to 3.

Examples of these substituents R ⁵ include alkyl groups such as cyclohexyl group, octyl group, lauryl group, stearyl group and dimethylene ether group, and heterocyclic groups such as 1H-benzotriazolemethylene group and N-phthalimidotetramethylene group. , Aromatic groups such as phenyl group, naphthalene group, biphenyl group and anthracenyl group. Among these, a phenyl group and a naphthalene group are more preferable.

In the general formula (1), the combinations of the substituents R ^{1 to} R ⁴ and R ⁵ are the substituents R ^{1 to} R ³ are each a methoxy group, R ⁴ is a trimethylene group, and R ⁵ is a benzene ring. Those which are groups are preferred. This has the advantage that it has excellent adhesion imparting properties and is inexpensive to manufacture.

  Such an organic silane compound (C) expresses good adhesion to the substrate without deteriorating the storage stability as compared with the conventional mercaptosilane compound.

  Here, a method for synthesizing the organosilane compound (C), that is, a method for synthesizing the organosilane compound represented by the general formula (1) will be described.

  Examples of the method for synthesizing the organic silane compound represented by the general formula (1) used in the present invention include an n-valent mercaptosilane compound such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane, and an n-valent compound. A compound having a triple bond such as an ethynyl group or an n-valent propargyl group can be obtained by heat reaction in a bulk or solvent, and the synthesis process is represented by the following formula (6). . By such a synthesis method, it is possible to synthesize easily and with high yield.

［式中、Ｒは、炭素数が１〜４のアルキル基、炭素数が１〜４のアルコキシ基、または炭素数が６〜１２のアリール基のいずれかを表し、互いに同一であっても異なっていてもよい。Ｒ'は、炭素数が１〜６の炭化水素基を表し、Ｒ’’はｎ価の有機基を表す。ｎは１〜３の整数を表す。］

[In the formula, R represents any of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. It may be. R ′ represents a hydrocarbon group having 1 to 6 carbon atoms, and R ″ represents an n-valent organic group. n represents an integer of 1 to 3. ]

  In the above synthesis step, preferably, the target silane compound can be obtained by subjecting a mercaptosilane compound and an ethynyl compound to a heat reaction at about 50 to 150 ° C. under bulk conditions. Such a reaction can be carried out in a solvent, but it is preferable to use a low-boiling solvent from the standpoint of product separation. Examples of the low boiling point solvent include acetone, methyl ethyl ketone, n-hexane, n-heptane, cyclohexane, tetrahydrofuran, toluene, chloroform, and the like, and one or more of these can be used in combination. . Examples of the mercaptosilane compound include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, and mercaptopropyldimethoxymethylsilane as described above. Examples of the compound having a triple bond include ethynylbenzene, 4-ethynyltoluene, ethynyl-4-methoxybenzene, ethynyl-4-nitrobenzene, 1-ethynylnaphthalene, 4-ethynylbiphenyl, 1-ethynylcyclopentanol, 1-ethynyl-1-cyclohexanol, α-ethynylbenzyl alcohol, 3 Monovalent ethynyl compounds such as ethynylpyridine, 1-propargyl-1H-benzotriazole, 6-phthalimido-1-hexyne, ethynyl-p-tolylsulfone and ethynyltrimethylsilane Divalent ethynyl compounds such as 1,3-diethynylbenzene, 1,5-diethynylnaphthalene, 9,10-diethynylanthracene, 1,3-diethynyltetramethyldisiloxane and dipropargyl ether and 1,3,5 -A trivalent ethynyl compound such as triethynylbenzene and the like.

  In the above reaction (formula (6)), the addition reaction can be further accelerated by increasing the molar ratio of the compound having a triple bond to the mercaptosilane compound. In such a case, unreacted raw materials may remain as long as the characteristics are not impaired, but the purity can be improved by separating and removing the raw materials and the solvent by distillation or the like as appropriate.

  The method for synthesizing the organosilane compound represented by the general formula (1) has a simple and general synthesis reaction route as described above, but is not limited thereto.

[Inorganic filler (D)]
The inorganic filler is blended (mixed) in the epoxy resin composition for the purpose of reinforcing the obtained semiconductor device, and there is no particular limitation on the type thereof, and it is generally used as a sealing material. Things can be used.

  Examples of the inorganic filler (D) include fused crushed silica, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay, and glass fiber. These can be used alone or in combination of two or more. Among these, fused silica is particularly preferable. Since fused silica is poor in reactivity with the curing accelerator of the present invention, it is possible to prevent the curing reaction of the epoxy resin composition from being inhibited even when a large amount is blended (mixed) in the epoxy resin composition. Can do. Moreover, the reinforcement effect of the semiconductor device obtained improves by using a fused silica as an inorganic filler (D).

  Moreover, as a shape of an inorganic filler (D), what kind of things, such as a granular form, a lump shape, and a scale shape, may be sufficient, for example, It is preferable that it is granular (especially spherical shape).

  In this case, the average particle diameter of the inorganic filler (D) is preferably about 1 to 100 μm, and more preferably about 5 to 35 μm. In this case, the particle size distribution is preferably wide. Thereby, the filling amount (usage amount) of the inorganic filler (D) can be increased, and the reinforcing effect of the obtained semiconductor device is further improved.

  In the epoxy resin composition of the present invention, the content (blending amount) of the organosilane compound (C) is not particularly limited, but is preferably about 0.01 to 10% by weight, preferably 0.1 to 5% by weight. More preferably, it is about. Thereby, the adhesion characteristic of an epoxy resin composition expresses preferably.

  Further, the compounding ratio of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule is not particularly limited. It is preferable that the phenolic hydroxyl group of the compound (B) is used in an amount of about 0.5 to 2 mol, and about 0.7 to 1.5 mol with respect to 1 mol of the epoxy group of (A). More preferably it is used. Thereby, various characteristics improve more, maintaining the balance of the various characteristics of an epoxy resin composition to a suitable thing.

  The content (blending amount) of the inorganic filler (D) is not particularly limited, but is about 200 to 2400 parts by weight per 100 parts by weight of the total amount of the compound (A) and the compound (B). It is preferable that the amount is about 400 to 1400 parts by weight. When content of an inorganic filler (D) is less than the said lower limit, there exists a possibility that the reinforcement effect by an inorganic filler (D) may not fully express, On the other hand, content of an inorganic filler (D) is the said upper limit. In the case of exceeding the above, the fluidity of the epoxy resin composition is lowered, and there is a possibility that poor filling or the like may occur when the epoxy resin composition is molded (for example, during manufacturing of a semiconductor device).

  In addition, if content (blending amount) of an inorganic filler (D) is 400-1400 weight part per 100 weight part of total amounts of the said compound (A) and the said compound (B), an epoxy resin composition The moisture absorption rate of the cured product becomes low, and the occurrence of solder cracks can be prevented. Since such an epoxy resin composition has good fluidity when heated and melted, it is preferably prevented from causing deformation of the gold wire inside the semiconductor device.

  In addition, the content (blending amount) of the inorganic filler (D) is based on the specific gravity of the compound (A), the compound (B) and the inorganic filler (D) itself, and the parts by weight are volume%. You may make it handle by converting.

[Curing accelerator (E)]
In the present invention, a curing accelerator can be added for the purpose of promoting the curing reaction of the compound (A) having two or more epoxy groups and the compound (B) having two or more phenolic hydroxyl groups in one molecule. The curing accelerator (E) is not limited as long as it has an action (function) that can accelerate the curing reaction of the epoxy resin composition.

Examples of these curing accelerators include triphenylphosphine, tris (4-tolyl) phosphine, tris (4-hydroxyphenyl) phosphine, tris (4-methylphenyl) phosphine, and tris (4-methoxyphenyl) phosphine). Tertiary phosphines, amidines such as 1,8-diazabicyclo (5,4,0) -7-undecene and 1,5-diazabicyclo (4,3,0) -5-nonene, 2-methylimidazole, 2- Examples include imidazoles such as phenylimidazole and 2-phenyl-4-methylimidazole, quaternary phosphonium salts such as tetraphenylphosphonium tetraphenylborate, and the like, which can be used alone or in combination of two or more.
In addition, the said hardening accelerator is an example and is not limited to these at all.

  In the epoxy resin composition of the present invention, the content (blending amount) of the curing accelerator (E) is not particularly limited, but is preferably about 0.01 to 1% by weight with respect to the entire composition. It is more preferably about 0.05 to 0.5% by weight. Thereby, the sclerosis | hardenability, preservability, fluidity | liquidity, and hardened | cured material characteristic of an epoxy resin composition are expressed with sufficient balance.

  In addition to the compounds (components) (A) to (D) and the component (E), the epoxy resin composition of the present invention may contain, for example, γ-glycidoxypropyl tri-propylene as necessary. Coupling agents such as methoxysilane, colorants such as carbon black, flame retardants such as brominated epoxy resins, antimony oxide and phosphorus compounds, low stress components such as silicone oil and silicone rubber, natural waxes, synthetic waxes, higher fatty acids or Various additives such as metal salts, mold release agents such as paraffin, and antioxidants may be blended (mixed).

  In the epoxy resin composition of the present invention, the compounds (components) (A) to (D) and the components (E) and, if necessary, other additives are mixed at room temperature using a mixer. It is obtained by heating and kneading using a hot roll, a heating kneader, etc., cooling and pulverizing.

  The epoxy resin composition of the present invention thus obtained is superior in storage stability as compared with an epoxy resin composition using a mercapto-based or amine-based coupling agent as an adhesion-imparting component. The reason is that the organosilane compound (C), which is an adhesion imparting component of the present invention, is inactive at low temperatures because the mercapto group having high reactivity with the epoxy group is thioesterified, and the curing reaction of the epoxy resin does not occur. This is because it is more difficult to proceed.

  The obtained epoxy resin composition is used as a molding resin, and is cured and molded by a molding method such as transfer molding, compression molding, and injection molding, thereby sealing an electronic component such as a semiconductor element. Thereby, the semiconductor device of the present invention is obtained.

  The form of the semiconductor device of the present invention is not particularly limited. For example, SIP (Single Inline Package), HSIP (SIP with Heatsink), ZIP (Zig-zag Inline Package), DIP (Dual Inline Package), SDIP (Shrink Dual Inline Package), SOP (Small Outline Package), SSOP (Shrink Small Outline Package), TSOP (Thin Small Outline Package), SOJ (Small Outline J-leaded Package), QFP (Quad Flat Package), QFP (FP) ) (QFP Fine Pitch), TQFP (Thin Quad Flat Package), QFJ (PLCC) (Quad Flat J-leaded Package), BGA (Ball Grid Array), and the like.

  The semiconductor device of the present invention thus obtained is excellent in solder crack resistance. The reason is excellent in the solder crack resistance because peeling occurs because the resin cured product by the organosilane compound (C) which is the adhesion imparting component of the present invention is excellent in adhesion to the substrate.

  Although this embodiment demonstrated the case where the epoxy resin composition of this invention was used as a sealing material of a semiconductor device, as an application of the epoxy resin composition of this invention, it is not limited to this. Moreover, according to the use etc. of an epoxy resin composition, in the epoxy resin composition of this invention, mixing (formulation) of an inorganic filler can also be abbreviate | omitted.

  The preferred embodiments of the epoxy resin composition and the semiconductor device of the present invention have been described above, but the present invention is not limited thereto.

  Next, specific examples of the present invention will be described.

  First, compounds C1 to C5 and mercaptopropyltrimethoxysilane used as curing accelerators were prepared.

(Synthesis of Compound C1)
Mercaptopropyltrimethoxysilane (19.6 g, 0.10 mol) and ethynylbenzene (10.2 g, 0.10 mol) were charged into a three-necked flask equipped with a stirrer and a cooling device (volume: 50 mL) and stirred uniformly at room temperature. It was set as the solution. The homogeneous solution was reacted at 100 ° C. for 24 hours with stirring. The reaction solution was distilled under reduced pressure of 50 Torr to remove the remaining raw materials, and finally 26.8 g of a light brown transparent liquid was obtained.

This compound was designated C1. As a result of analyzing the compound C1 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target silane compound represented by the following formula (7). The yield of the obtained compound C1 was 90%.

(Synthesis of Compound C2)
19.6 g (0.10 mol) of mercaptopropyltrimethoxysilane and 13.2 g (0.10 mol) of 1-ethynyl-4-methoxybenzene are charged into a three-necked flask (volume: 50 mL) equipped with a stirrer and a cooling device. The mixture was stirred at room temperature to obtain a uniform solution. The homogeneous solution was reacted at 100 ° C. for 24 hours with stirring. The reaction solution was distilled under reduced pressure of 10 Torr to remove the remaining raw materials, and finally 28.9 g of a pale yellow transparent liquid was obtained.

This compound was designated C2. As a result of analyzing the compound C2 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target silane compound represented by the following formula (8). The yield of the obtained compound C2 was 88%.

(Synthesis of Compound C3)
19.6 g (0.10 mol) of mercaptopropyltrimethoxysilane and 15.2 g (0.10 mol) of 1-ethynylnaphthalene were charged into a three-necked flask (volume: 50 mL) equipped with a stirrer and a cooling device and stirred at room temperature. A homogeneous solution was obtained. The homogeneous solution was reacted at 100 ° C. for 24 hours with stirring. The reaction solution was distilled under reduced pressure of 10 Torr to remove the remaining raw materials, and finally 30.3 g of a light brown transparent liquid was obtained.

This compound was designated as C3. As a result of analyzing the compound C3 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target silane compound represented by the following formula (9). The yield of the obtained compound C3 was 87%.

(Synthesis of Compound C4)
19.6 g (0.10 mol) of mercaptopropyltrimethoxysilane and 4.7 g (0.05 mol) of mercaptopropyltrimethoxysilane were charged into a three-necked flask (volume: 50 mL) equipped with a stirrer and a cooling device, and stirred at room temperature. A homogeneous solution was obtained. The homogeneous solution was reacted at 100 ° C. for 24 hours with stirring. The reaction solution was distilled under reduced pressure of 10 Torr to remove the remaining raw materials, and finally, 19.7 g of a pale yellow transparent liquid was obtained.

This compound was designated as C4. As a result of analyzing the compound C4 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target silane compound represented by the following formula (10). The yield of the obtained compound C4 was 81%.

(Synthesis of Compound C5)
A three-necked flask (volume: 50 mL) equipped with a stirrer and a cooling device was charged with 19.6 g (0.10 mol) of mercaptopropyltrimethoxysilane and 6.3 g (0.05 mol) of 1,3-diethynylbenzene, Stir at room temperature to make a homogeneous solution. The homogeneous solution was reacted at 100 ° C. for 24 hours with stirring. The reaction solution was distilled under reduced pressure of 10 Torr to remove the remaining raw materials, and finally 23.8 g of a light brown transparent liquid was obtained.

This compound was designated as C5. Compound C5 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed that it was the target silane compound represented by the following formula (11). The yield of the obtained compound C5 was 92%.

  Further, triphenylphosphine and 1,8-diazabicyclo [5.4.0] -7-undecene were prepared as curing accelerators.

[Preparation of epoxy resin composition and manufacture of semiconductor device]
An epoxy resin composition containing the compounds C1 to C5, mercaptopropyltrimethoxysilane, triphenylphosphine, and 1,8-diazabicyclo [5.4.0] -7-undecene was prepared as follows, and a semiconductor device Manufactured.

(Example 1)
First, a biphenyl type epoxy resin (YX-4000HK manufactured by Japan Epoxy Resin Co., Ltd.) represented by the following formula (12) as the compound (A), and a phenol aralkyl resin represented by the following formula (13) as the compound (B). (However, the number of repeating units: 3 represents an average value. XLC-LL manufactured by Mitsui Chemicals, Inc.) Compound C1 as an adhesion-imparting component (organosilane compound (C)), and compound tri as a curing accelerator (D). Phenylphosphine, fused spherical silica (average particle size 15 μm) as inorganic filler (E), and carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared as other additives, respectively.

＜式（１２）で表される化合物の物性＞
融点 ：１０５℃
エポキシ当量 ：１９３
１５０℃のＩＣＩ溶融粘度：０．１５ｐｏｉｓｅ

<Physical Properties of Compound Represented by Formula (12)>
Melting point: 105 ° C
Epoxy equivalent: 193
ICI melt viscosity at 150 ° C .: 0.15 poise

＜式（１３）で表される化合物の物性＞
軟化点 ：７７℃
水酸基当量 ：１７２
１５０℃のＩＣＩ溶融粘度：３．６ｐｏｉｓｅ

<Physical Properties of Compound Represented by Formula (13)>
Softening point: 77 ° C
Hydroxyl equivalent: 172
ICI melt viscosity at 150 ° C .: 3.6 poise

  Next, the biphenyl type epoxy resin: 52 parts by weight, the phenol aralkyl resin: 48 parts by weight, compound C1: 2.98 parts by weight, triphenylphosphine: 1.00 parts by weight, fused spherical silica: 730 parts by weight, carbon Black: 2 parts by weight, brominated bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight are first mixed at room temperature, then kneaded at 95 ° C. for 8 minutes using a hot roll, and then cooled and ground. Thus, an epoxy resin composition was obtained.

  Next, using this epoxy resin composition as a mold resin, 8 100-pin TQFP packages (semiconductor devices) and 15 16-pin DIP packages (semiconductor devices) were produced, respectively.

  The 100-pin TQFP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 7.4 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.

  The package size of the 100-pin TQFP was 14 × 14 mm, the thickness was 1.4 mm, the silicon chip (semiconductor element) size was 8.0 × 8.0 mm, and the lead frame was 42 alloy.

  The 16-pin DIP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.

  The package size of the 16-pin DIP is 6.4 × 19.8 mm, the thickness is 3.5 mm, the silicon chip (semiconductor element) size is 3.5 × 3.5 mm, and the lead frame is made of 42 alloy. .

(Example 2)
First, as a compound (A), a biphenyl aralkyl type epoxy resin represented by the following formula (14) (however, the number of repeating units: 3 shows an average value. NC-3000P manufactured by Nippon Kayaku Co., Ltd.), a compound ( B) a biphenylaralkyl type phenol resin represented by the following formula (15) (however, the number of repeating units: 3 represents an average value. MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.), adhesion imparting component (organosilane compound) (C)), curing accelerator (triphenylphosphine), fused spherical silica (average particle size 15 μm) as inorganic filler (E), carbon black, brominated bisphenol A type epoxy resin and carnauba wax as other additives. , Each prepared.

＜式（１４）で表される化合物の物性＞
軟化点 ：６０℃
エポキシ当量 ：２７２
１５０℃のＩＣＩ溶融粘度：１．３ｐｏｉｓｅ

<Physical Properties of Compound Represented by Formula (14)>
Softening point: 60 ° C
Epoxy equivalent: 272
ICI melt viscosity at 150 ° C .: 1.3 poise

＜式（１５）で表される化合物の物性＞
軟化点 ：６８℃
水酸基当量 ：１９９
１５０℃のＩＣＩ溶融粘度：０．９ｐｏｉｓｅ

<Physical properties of the compound represented by the formula (15)>
Softening point: 68 ° C
Hydroxyl equivalent: 199
ICI melt viscosity at 150 ° C .: 0.9 poise

  Next, said biphenyl aralkyl type epoxy resin: 57 parts by weight, said biphenyl aralkyl type phenol resin: 43 parts by weight, compound C1: 2.98 parts by weight, triphenylphosphine: 1.00 parts by weight, fused spherical silica: 650 parts by weight Part, carbon black: 2 parts by weight, brominated bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight, first kneaded at room temperature and then kneaded at 105 ° C. for 8 minutes using a hot roll, The mixture was cooled and pulverized to obtain an epoxy resin composition (thermosetting resin composition).

  Next, using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

Example 3
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 3.28 parts by weight of compound C2 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.

Example 4
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 3.28 parts by weight of compound C2 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.

(Example 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 3.48 parts by weight of compound C3 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.

(Example 6)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 3.48 parts by weight of compound C3 was used instead of compound C1, and this epoxy resin composition was used. A package (semiconductor device) was manufactured.

(Example 7)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 2.43 parts by weight of compound C4 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.

(Example 8)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 2.43 parts by weight of compound C4 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.

Example 9
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 2.59 parts by weight of compound C5 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 1, a package (semiconductor device) was manufactured.

(Example 10)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that 2.59 parts by weight of compound C5 was used instead of compound C1, and this epoxy resin composition was used. In the same manner as in Example 2, a package (semiconductor device) was manufactured.

(Example 11)
An epoxy resin composition (thermosetting) was carried out in the same manner as in Example 1 except that 1,8-diazabicyclo [5.4.0] -7-undecene: 0.60 parts by weight was used instead of triphenylphosphine. The resin composition was obtained, and a package (semiconductor device) was manufactured in the same manner as in Example 1 using this epoxy resin composition.

(Example 12)
An epoxy resin composition (thermosetting) was conducted in the same manner as in Example 2 except that 1,8-diazabicyclo [5.4.0] -7-undecene: 0.60 parts by weight was used instead of triphenylphosphine. Resin package), and using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 2.

(Comparative Example 1)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that mercaptopropyltrimethoxysilane: 1.96 parts by weight was used instead of compound C1, and this epoxy resin composition was obtained. Using the product, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Comparative Example 2)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that mercaptopropyltrimethoxysilane: 1.96 parts by weight was used instead of compound C1, and this epoxy resin composition was obtained. Using the product, a package (semiconductor device) was manufactured in the same manner as in Example 2.

(Comparative Example 3)
Except that instead of compound C1, mercaptopropyltrimethoxysilane: 1.96 parts by weight and 1,8-diazabicyclo [5.4.0] -7-undecene: 0.60 parts by weight instead of triphenylphosphine were used. Then, an epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1, and a package (semiconductor device) was produced in the same manner as in Example 1 by using this epoxy resin composition. .

(Comparative Example 4)
Except that instead of compound C1, mercaptopropyltrimethoxysilane: 1.96 parts by weight and 1,8-diazabicyclo [5.4.0] -7-undecene: 0.60 parts by weight instead of triphenylphosphine were used. Then, an epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2, and a package (semiconductor device) was produced in the same manner as in Example 2 by using this epoxy resin composition. .

[Characteristic evaluation]
Characteristic evaluation (1) to (3) of the epoxy resin composition obtained in each example and each comparative example, and characteristic evaluation (4) and (5) of the semiconductor device obtained in each example and each comparative example ) Was performed as follows.

(1): Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, measurement was performed at a mold temperature of 175 ° C, an injection pressure of 6.8 MPa, and a curing time of 2 minutes.

  This spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.

(2): Curing torque Using a curast meter (Orientec Co., Ltd., JSR curast meter IV PS type), the torque after 175 ° C. and 45 seconds was measured.
This hardening torque shows that curability is so favorable that a numerical value is large.

(3): Flow residual ratio After the obtained epoxy resin composition was stored in the atmosphere at 30 ° C for 1 week, the spiral flow was measured in the same manner as in (1) above, and the percentage (% )
This flow residual ratio indicates that the larger the numerical value, the better the storage stability.

(4): Solder crack resistance 100-pin TQFP was humidified for 168 hours in an environment of 85 ° C. and 85% relative humidity, and then heat-treated in an IR reflow furnace at a maximum temperature of 260 ° C. for 2 minutes.

  Then, the presence or absence of the occurrence of external cracks was observed under a microscope, and displayed as a percentage (%) as crack generation rate = (number of packages in which cracks occurred) / (total number of packages) × 100.

  Further, the ratio of the peeled area between the silicon chip and the cured product of the epoxy resin composition was measured using an ultrasonic flaw detector, and the peel rate = (peeled area) / (silicon chip area) × 100. The average value of the package was obtained and expressed as a percentage (%).

  These crack generation rate and peel rate indicate that the smaller the numerical value, the better the solder crack resistance.

(5): Moisture resistance reliability A voltage of 20 V was applied to a 16-pin DIP in water vapor at 125 ° C. and a relative humidity of 100%, and disconnection defects were examined. The time until a defect appears in 8 or more of the 15 packages was defined as a defect time.

Note that the measurement time is 500 hours at the longest, and when the number of defective packages is less than 8 at that time, the defective time is indicated as over 500 hours (> 500).
This failure time indicates that the larger the numerical value, the better the moisture resistance reliability.
Table 1 shows the results of the characteristic evaluations (1) to (5).

  As shown in Table 1, all of the epoxy resin compositions (epoxy resin compositions of the present invention) obtained in Examples 1 to 12 have better storage stability than the comparative examples, and further this curing. Each of the packages of the embodiments (semiconductor device of the present invention) sealed with an object had good solder crack resistance.

  On the other hand, all of the epoxy resin compositions obtained in Comparative Examples 1 to 4 were inferior in storage stability as compared with the Examples.

(Examples 13 to 18, Comparative Examples 5 and 6)
As the compound (A), the biphenyl type epoxy resin represented by the formula (12): 26 parts by weight, the biphenyl aralkyl type epoxy resin represented by the formula (14): 28.5 parts by weight, and the compound (B) ), Except for blending 45.5 parts by weight of the phenol aralkyl resin represented by the formula (13), respectively, Examples 1, 3, 5, 7, 9, 11, and Comparative Examples 1, 3 and Similarly, an epoxy resin composition (thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured using this epoxy resin composition.

  When the characteristics of the epoxy resin compositions and packages obtained in Examples 13 to 18 and Comparative Examples 5 and 6 were evaluated in the same manner as described above, the same results as in Table 1 were obtained.

(Examples 19 to 24, Comparative Examples 7 and 8)
As compound (A), biphenyl type epoxy resin represented by the formula (12): 54.5 parts by weight, as compound (B), phenol aralkyl resin represented by the formula (13): 24 parts by weight, and Biphenyl aralkyl type phenol resin represented by the formula (15): Except for blending 21.5 parts by weight, Examples 1, 3, 5, 7, 9 and 11 and Comparative Examples 1 and 3, respectively, Similarly, an epoxy resin composition (thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured using this epoxy resin composition.

  When the characteristics of the epoxy resin compositions and packages obtained in Examples 19 to 24 and Comparative Examples 7 and 8 were evaluated in the same manner as described above, almost the same results as in Table 1 were obtained.

  By using such an epoxy resin composition, an epoxy resin composition having good curability, storage stability and fluidity can be obtained. This epoxy resin can be suitably used in the field of electrical and electronic materials, and in particular, to obtain an electronic component device in which an electronic component such as a semiconductor element excellent in solder crack resistance and moisture resistance reliability is sealed. Can do.

Claims (6)

Essentially a compound (A) having two or more epoxy groups in one molecule, a compound (B) having two or more phenolic hydroxyl groups in one molecule, and an organosilane compound (C) represented by the general formula (1) An epoxy resin composition, characterized by comprising a component.

[Wherein R ¹ , R ² and R ³ represent any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, They may be the same or different. R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms, and R ⁵ represents an n-valent organic group. n represents an integer of 1 to 3. ] The compound (A) having two or more epoxy groups in one molecule is mainly composed of at least one of an epoxy resin represented by the following general formula (2) and an epoxy resin represented by the following general formula (3). The epoxy resin composition according to claim 1.

[Wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ each represent one selected from a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, They may be the same or different. ]

[Wherein, R ^{10 to} R ¹⁷ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, a is an integer of 1-10. ] The compound (B) having two or more phenolic hydroxyl groups in one molecule is mainly composed of at least one of a phenol resin represented by the following general formula (4) and a phenol resin represented by the following general formula (5). The epoxy resin composition according to claim 1 or 2.

[Wherein, R ^{18 to} R ²¹ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, b is an integer of 1-10. ]

[Wherein, R ^{22 to} R ²⁹ each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same as or different from each other. However, c is an integer of 1-10. ]   The epoxy resin composition in any one of Claims 1-3 containing an inorganic filler (D).   The content of the inorganic filler is 100 weights in total of the compound (A) having two or more epoxy groups in one molecule and the compound (B) having two or more phenolic hydroxyl groups in one molecule. The epoxy resin composition according to claim 4, which is 200 to 2400 parts by weight per part.   An electronic component is sealed with a cured product of the epoxy resin composition according to claim 5.